Effects of radial injection and solution thickness on the dynamics of confined A + B → C chemical fronts.

The spatio-temporal dynamics of an A + B → C front subjected to radial advection is investigated experimentally in a thin solution layer confined between two horizontal plates by radially injecting a solution of potassium thiocyanate (A) into a solution of iron(iii) nitrate (B). The total amount and spatial distribution of the product FeSCN2+ (C) are measured for various flow rates Q and solution thicknesses h. The long-time evolution of the total amount of product, nC, is compared to a scaling obtained theoretically from a one-dimensional reaction-diffusion-advection model with passive advection along the radial coordinate r. We show that, in the experiments, nC is significantly affected when varying either Q or h but scales as nC∼Q-1/2V where V is the volume of injected reactant A provided the solution thickness h between the two confining plates is sufficiently small, in agreement with the theoretical prediction. Our experimental results also evidence that the temporal evolution of the width of the product zone, WC, follows a power law, the exponent of which varies with both Q and h, in disagreement with the one-dimensional model that predicts WC∼t1/2. We show that this experimental observation can be rationalized by taking into account the non-uniform profile of the velocity field of the injected reactant within the cell gap.

Directional coupling in spatially distributed nanoreactors.

Silica based hollow nanospheres filled with a reactant solution act as nanoreactors. A close packed ensemble of the nanoshells comprise a porous medium through which a chemical front can propagate. The front velocity decreases as the chemical signal, in the shape of a reaction-diffusion front, is transmitted from one sphere to the other due to the high curvature at the contact points. Experiments reveal that front propagation occurs through the cavity of the nanoshells because surface activity of filled nanoparticles itself cannot support chemical front across the medium.

Macroscale precipitation kinetics: towards complex precipitate structure design.

Producing self-assembled inorganic precipitate micro- and macro-structures with tailored properties may pave the way for new possibilities in, e.g., materials science and the pharmaceutical industry. One set of important parameters to maintain appropriate control over the yield falls in the frame of reaction kinetics, which affects the possible coupling between hydrodynamics and chemical reactions under flow conditions. In this study, we present a spectrophotometric method to experimentally determine the characteristic timescales of precipitation reactions. It is also shown that the nickel-oxalate model system - despite the fast chemical complexation equilibria taking place - can be kinetically described by either Classical Nucleation Theory or the classical homogeneous kinetics approach. The applicability of our results is illustrated via injection experiments intrinsically exhibiting coupling between chemistry and hydrodynamics. Therefore, we suggest that easy-to-handle power law functions may be applied to characterize the precipitation kinetics in flow systems.

Interaction between amino-functionalized inorganic nanoshells and acid-autocatalytic reactions.

Amino-functionalized inorganic silica nanoshells with a diameter of 511 ± 57 nm are efficiently used as hydrogen ion binders with a base dissociation constant of (1.2 ± 0.1) × 10-4. The hydrogen removal has been shown to produce reaction-diffusion fronts of constant propagation velocity in the autocatalytic chlorite-tetrathionate reaction when it is run in thin planar slices of nanoshell-containing agarose gel to exclude all convection related effects. By controlling the exact amount of amino-functionalized hollow nanospheres in the gel matrix it is possible to finely tune the propagation velocity of the chemical front in the 0.1-10 cm h-1 range. Remarkably, this can be achieved with very low amino-functionalized hollow inorganic nanosphere loadings between 0.1-0.01 (m V-1)%. The front width has also been determined experimentally, which increases by a factor of two with one magnitude decrease in the front velocity.

Spirals in a reaction-diffusion system: Dependence of wave dynamics on excitability.

A detailed study of the effects of excitability of the Belousov-Zhabotinsky (BZ) reaction on spiral wave properties has been carried out. Using the Oregonator model, we explore the various regimes of wave activity, from sustained oscillations to wave damping, as the system undergoes a Hopf bifurcation, that is achieved by varying the excitability parameter, ε. We also discover a short range of parameter values where random oscillations are observed. With an increase in the value of ε, the frequency of the wave decreases exponentially, as the dimension of the spiral core expands. These numerical results are confirmed by carrying out experiments in thin layers of the BZ system, where the excitability is changed by varying the concentrations of the reactant species. Effect of reactant concentrations on wave properties like time period and wavelength are also explored in detail. Drifting and meandering spirals are found in the parameter space under investigation, with the excitability affecting the tip trajectory in a way predicted by the numerical studies. This study acts as a quantitative evidence of the relationship between the excitability parameter, ε, and the substrate concentrations.

Controlling three-dimensional vortices using multiple and moving external fields.

Spirals or scroll wave activities in cardiac tissues are the cause of lethal arrhythmias. The external control of these waves is thus of prime interest to scientists and physicians. In this article, we demonstrate the spatial control of scroll waves by using external electric fields and thermal gradients in experiments with the Belousov-Zhabotinsky reaction. We show that a scroll ring can be made to trace cyclic trajectories under a rotating electric field. Application of a thermal gradient in addition to the electric field deflects the motion and changes the nature of the trajectory. Our experimental results are analyzed and corroborated by numerical simulations based on an excitable reaction diffusion model.

Interaction of scroll waves in an excitable medium: Reconnection and repulsion.

Scroll waves of reentrant activity and their interactions pose a serious threat to cardiac health. In experiments with the Belousov-Zhabotinsky reaction we demonstrate the interaction of scroll waves. We show that depending on their mutual orientation, two scroll rings can push each other away and rupture on touching the system boundary, or they can reconnect to form a single, large ring. Reconnection only occurs when the filaments lie within one core length of each other. The reconnected filament has extended lifetimes, which could have serious implications in systems where they occur. The experimental results are explained on the basis of a simple numerical model.

Unpinning of scroll waves under the influence of a thermal gradient.

Three-dimensional scroll waves of electrical activity are among the mechanisms believed to be responsible for the rapid, unsynchronized contraction of cardiac ventricles, thereby reducing the heart's ability to pump blood. Scroll waves can attach themselves to unexcitable obstacles, and this sometimes highly elongates their life span. Hence, the unpinning and annihilation of these vortices has attracted much attention in recent decades. In this work, we study the influence of a thermal gradient on scroll waves pinned to inert obstacles, in the Belousov-Zhabotinsky reaction. Under a temperature gradient, scroll rings were seen to unpin from these obstacles, thus strikingly reducing their lifetimes. These results were also reproduced by numerical simulations using the Barkley model.